Polysaccharide derivative and separating agent for optical isomer containing the same

a technology of optical isomer and separating agent, which is applied in the direction of sugar derivates, instruments, organic racemisation, etc., can solve problems such as difficult to distinguish, and achieve the effect of excellent optical isomer separating ability

Inactive Publication Date: 2009-10-22
DAICEL CHEM IND LTD +1
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AI Technical Summary

Benefits of technology

[0035]In addition, the present invention is additionally effective from the viewpoint of the provision of a polysaccharide derivative excellent in optical isomer separating ability and suitable for a separating agent for optical isomers when the polysaccharide is amylose.
[0036]In addition, the present invention provides a method including the steps of: modifying a hydroxyl group or amino group at the 2-position of each of the structural units of a polysaccharide with a first substituent represented by any one of the general formulae (I) to (III); and modifying a hydroxyl group or amino group at the 3-position of the structural unit with a second substituent represented by any one of the general formulae (I) to (III) and different from the first substituent. Accordingly, there can be provided a polysaccharide derivative excellent in optical isomer separating ability and suitable for a separating agent for optical isomers.
[0038]In addition, the present invention is additionally effective from the viewpoint of the provision of a polysaccharide derivative excellent in optical isomer separating ability and suitable for a separating agent for optical isomers when the structural units are each a hexose further having a hydroxyl group or amino group at its 6-position, and the method further includes the step of protecting the hydroxyl group or amino group at the 6-position with a protective group after the modification of the hydroxyl group or amino group at the 2-position.
[0040]In addition, the present invention provides a method including: a 2-position protecting step of protecting a hydroxyl group or amino group at the 2-position of each of the structural units of a polysaccharide with a protective group; a 3-position modifying step of modifying a hydroxyl group or amino group at the 3-position of the structural unit the 2-position of which has been protected with a second substituent represented by any one of the general formulae (I) to (III); a 2-position deprotecting step of removing the protective group at the 2-position in the structural unit the 3-position of which has been modified; and a 2-position modifying step of modifying the hydroxyl group or amino group at the 2-position from which the protective group has been removed with a first substituent represented by the same general formula as that of the second substituent but different from the second substituent. Accordingly, there can be provided a polysaccharide derivative excellent in ability to separate optical isomers each having a structure in which it is difficult to introduce substituents at 2- and 3-positions accurately, and suitable for a separating agent for optical isomers.
[0044]In addition, the present invention is additionally effective from the viewpoint of the provision of a polysaccharide derivative obtained by introducing different substituents into the 2-, 3-, and 6-positions of a hexose, excellent in optical isomer separating ability, and suitable for a separating agent for optical isomers when the structural units are each a hexose further having a hydroxyl group or amino group at its 6-position, the method further includes, between the 2-position protecting step and the 3-position modifying step, a 6-position protecting step of protecting the hydroxyl group or amino group at the 6-position of the structural unit the 2-position of which has been protected with a protective group before the 3-position modifying step, and further includes, between the 3-position modifying step and the 2-position deprotecting step, a 6-position deprotecting step of deprotecting the protective group at the 6-position in the structural unit the 3-position of which has been modified before the 2-position deprotecting step and a 6-position modifying step of modifying the hydroxyl group or amino group at the 6-position from which the protective group has been removed with a third substituent represented by the same general formula as that of each of the first and second substituents but different from the first and second substituents, and the 2-position deprotecting step is a step of removing the protective group at the 2-position in the structural unit the 6-position of which has been modified.
[0046]In addition, the present invention provides a separating agent for optical isomers containing the polysaccharide derivative. Accordingly, there can be provided a separating agent for optical isomers containing a polysaccharide derivative excellent in optical isomer separating ability and suitable for a separating agent for optical isomers.

Problems solved by technology

However, a polysaccharide derivative having a specific kind of a substituent at a specific position, in particular a polysaccharide derivative having specific substituents different from each other at its 2- and 3-positions that are hard to distinguish in the introduction of a substituent into a hexose leaves room for future studies.

Method used

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  • Polysaccharide derivative and separating agent for optical isomer containing the same
  • Polysaccharide derivative and separating agent for optical isomer containing the same
  • Polysaccharide derivative and separating agent for optical isomer containing the same

Examples

Experimental program
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synthesis example 1

Synthesis of 2-O-benzoyl amylose

[0115]

[0116]After 1.01 g (6.23 mmol, number average degree of polymerization: 300) of amylose had been dissolved in 20 mL of dehydrated dimethyl sulfoxide (DMSO), vinyl benzoate (2.3 mol / mol Anhydroglucose unit) and disodium hydrogen phosphate (2 mass % with respect to amylose) were added to the solution. The mixture was shielded from light with aluminum foil, and was then subjected to a reaction at 40° C. for 168.5 hours. After the completion of the reaction, a 2-propanol (IPA)-insoluble portion was filtrated with a glass filter, whereby Intermediate Product 1-1 as a white compound was obtained. In addition, synthesis was performed in the same manner as in the foregoing under various conditions shown in Table 1 below, whereby Intermediate Products 1-2 and 1-3 were obtained. The contents of investigations on reaction conditions in Intermediate Products 1-1 to 1-3 and the results of the investigations are shown below. In addition, FIG. 1 shows the 1H N...

synthesis example 2

Synthesis of amylose 2-benzoate-6-(3,5-dichlorophenylcarbamate)-3-(3,5-dimethylphenylcarbamate

[0117](1) Protection of 6-position with 4-methoxytrityl chloride

[0118]1.00 g (3.76 mmol) of Intermediate Product 1-1 was added to and dissolved in 20 mL of dehydrated pyridine. After that, 3.48 g (11.3 mmol) of 4-methoxytrityl chloride were added to the solution, and the mixture was subjected to a reaction at 70° C. for 24 hours. After the completion of the reaction, a methanol-insoluble portion was filtrated with a glass filter, whereby Intermediate Product 2-1 as a white compound was obtained. FIG. 2 shows the 1H NMR spectrum of Intermediate Product 2-1 thus obtained.

(2) Introduction of 3,5-dimethylphenylcarbamoyl group into 3-position

[0119]20 mL of pyridine and 0.50 g (3.36 mmol) of 3,5-dimethylphenyl isocyanate were added to 0.90 g (1.68 mmol) of Intermediate Product 2-1, and the mixture was subjected to a reaction at 80° C. for 15 hours. After the completion of the reaction, a methanol...

synthesis example 3

Synthesis of amylose 2-benzoate-3-(3,5-dichlorophenylcarbamate)-6-(3,5-dimethylphenylcarbamate

[0126](1) Introduction of 3,5-dichlorophenylcarbamoyl group into 3-position

[0127]Synthesis was performed in the same manner as in the section (2) of Synthesis Example 2 under conditions in the foregoing chemical formula except that: Intermediate Product 2-1 was changed to Intermediate Product 3-1; and 3,5-dimethylphenyl isocyanate was changed to 3,5-dichlorophenyl isocyanate. Thus, Intermediate Product 3-2 as a white compound was obtained. The yield of Intermediate Product 3-2 thus obtained was 0.64 g (96.6%). In addition, FIG. 6 shows the 1H NMR spectrum of Intermediate Product 3-2 thus obtained.

[0128](2) Deprotection of 4-methoxytrityl group at 6-position

[0129]Synthesis was performed in the same manner as in the section (3) of Synthesis Example 2 under conditions in the foregoing chemical formula, whereby Intermediate Product 3-3 as a white compound was obtained. The yield and physical pr...

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Abstract

The present invention provides: a polysaccharide derivative containing a structure wherein hydrogen atoms in a hydroxyl group or amino group at the 2-position and the 3-position of a structure unit of polysaccharide are substituted with different substituents respectively represented by a specific general formula; and, a separating agent for optical isomers, which contains such a polysaccharide derivative. The present invention can provide a novel polysaccharide derivative which has excellent optical isomer separating ability, and is thus suitable for a separating agent for optical isomers, and can provide a separating agent for optical isomers which comprises the polysaccharide derivative.

Description

TECHNICAL FIELD[0001]The present invention relates to a polysaccharide derivative useful in separating optical isomers, and a separating agent for optical isomers containing the polysaccharide derivative.BACKGROUND ART[0002]A polysaccharide derivative obtained by modifying the hydroxyl groups or amino groups of a polysaccharide with various substituents is known to serve as a chiral stationary phase in chromatography to show a high optical resolution, and a large number of kinds of polysaccharide derivatives have been heretofore synthesized.[0003]Examples of such polysaccharide derivative useful as a separating agent for optical isomers include: an ester derivative of a polysaccharide (see, for example, Patent Document 1); an alkyl-substituted phenylcarbamate of a polysaccharide except cellulose (see, for example, Patent Document 2); a chitosan derivative (see, for example, Patent Document 3); a cyclodextrin derivative (see, for example, Patent Document 4); a polysaccharide derivati...

Claims

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Application Information

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IPC IPC(8): C08B37/00C07H1/00
CPCB01J20/262B01J20/265B01J20/285B01J20/286B01J20/29C08B33/06B01J20/328C07B57/00C08B33/00C08B33/02C08B33/04B01J20/3272G01N30/88
InventorOKAMOTO, YOSHIOYAMAMOTO, CHIYOKONDO, SHUNSUKEKAMIGAITO, MASAMI
OwnerDAICEL CHEM IND LTD